物理化学学报 >> 2022, Vol. 38 >> Issue (6): 2106010.doi: 10.3866/PKU.WHXB202106010

所属专题: 面向电化学储能与转化的表界面工程

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海水电解面临的挑战与机遇:含氯电化学中先进材料研究进展

崔柏桦1,2, 施毅2, 李根3, 陈亚楠3,*(), 陈伟1,2,4, 邓意达3,5,*(), 胡文彬1,3,*()   

  1. 1 新加坡国立大学-天津大学联合学院,天津大学国际校区,福州 350207
    2 新加坡国立大学化学系,新加坡 117543
    3 天津大学材料科学与工程学院,天津 300350
    4 新加坡国立大学物理系,新加坡 117542
    5 海南大学材料科学与工程学院,海口,570228
  • 收稿日期:2021-06-03 录用日期:2021-07-12 发布日期:2021-07-21
  • 通讯作者: 陈亚楠,邓意达,胡文彬 E-mail:yananchen@tju.edu.cn;yida.deng@tju.edu.cn;wbhu@tju.edu.cn
  • 作者简介:Yanan Chen is a professor at the School of Materials Science and Engineering, Tianjin University. He received his joint Ph.D. from the University of Science and Technology Beijing/University of Maryland in 2017. He was an advanced innovative fellow at Tsinghua University before joining in Tianjin University. His research mainly focuses on nanomaterials, devices, and systems for advanced energy storage and conversion
    Yida Deng is a professor in School of Materials Science and Engineering, Tianjin University. He received his Ph.D. from Shanghai Jiao Tong University in 2006. His research interests include metal and metal oxide nanostructures for electrochemical and energy applications
    Wenbin Hu is a professor and Dean of the School of Materials Science and Engineering at Tianjin University. Prior to joining Tianjin University, he worked as a professor in Department of Materials Science and Engineering at Shanghai Jiao Tong University. He graduated from Central South University with a B.Sc. in 1988. Then he received M.Sc. from Tianjin University in 1991 and Ph.D. from Central South University in 1994. His research interests focus on design, synthesis and characterization of advanced micro/nanomaterials for energy storage and conversion applications, which was supported by the National Science Foundation for Distinguished Young Scholars of China
  • 基金资助:
    国家重点研发计划培育项目(2018YFB0703500);国家自然科学基金(91963113);新加坡国立大学绿色能源旗舰项目

Challenges and Opportunities for Seawater Electrolysis: A Mini-Review on Advanced Materials in Chlorine-Involved Electrochemistry

Baihua Cui1,2, Yi Shi2, Gen Li3, Yanan Chen3,*(), Wei Chen1,2,4, Yida Deng3,5,*(), Wenbin Hu1,3,*()   

  1. 1 Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou 350207, China
    2 Department of Chemistry, National University of Singapore, Singapore 117543, Singapore
    3 School of Materials Science and Engineering, Tianjin University, Tianjin 300350, China
    4 Department of Physics, National University of Singapore, Singapore 117542, Singapore
    5 School of Materials Science and Engineering, Hainan University, Haikou 570228, China
  • Received:2021-06-03 Accepted:2021-07-12 Published:2021-07-21
  • Contact: Yanan Chen,Yida Deng,Wenbin Hu E-mail:yananchen@tju.edu.cn;yida.deng@tju.edu.cn;wbhu@tju.edu.cn
  • About author:E-mail: yida.deng@tju.edu.cn (Y. D.)
    E-mail: wbhu@tju.edu.cn(W.H.)
    E-mail: yananchen@tju.edu.cn (Y.C.)
  • Supported by:
    the National Key Research and Development Program of China(2018YFB0703500);the National Natural Science Foundation of China(91963113);the NUS Flagship Green Energy Programme

摘要:

氢气是一种清洁高效的能源载体,通过海水电解规模化制备氢气能够为应对全球能源挑战提供新的机遇。然而,缺乏高活性、高选择性和高稳定性的理想电极材料是在腐蚀性海水中连续电解过程的一个巨大挑战。为了缓解这一困境,需要从基础理论和实际应用两方面对材料进行深入研究。近年来,人们围绕电极材料的催化活性、选择性和耐腐蚀性进行了大量的探索。本文重点总结了高选择性和强耐腐蚀性材料的设计合成与作用机制。其中详细介绍了多种电极材料(如多金属氧化物、Ni/Fe/Co基复合材料、氧化锰包覆异质结构等)对氧气生成选择性的研究进展;系统论述了各种材料的抗腐蚀工程研究成果,主要讨论了本征抗腐蚀材料、外防护涂层和原位产生抗腐蚀物种三种情况。此外,提出了海水电解过程中存在的挑战和潜在的机遇。先进纳米材料的设计有望为解决海水电解中的氯化学问题提供新思路。

关键词: 海水电解, 氯化学, 抗腐蚀, 选择性催化剂

Abstract:

Hydrogen (H2) is an important component in the framework of carbon-neutral energy, and the scalable production of H2 from seawater electrolysis offers a feasible route to address global energy challenges. With abundant seawater reserves, seawater electrolysis, especially when powered by renewable electricity sources, has great prospects. However, chloride ions (Cl-) in seawater can participate in the anodic reaction and accelerate the corrosion of electrode materials during electrolysis. Although the oxygen evolution reaction (OER) is thermodynamically favorable, the chlorine evolution reaction is highly competitive because fewer electrons are involved (2e-). These two problems are compounded by the dearth of corrosion-resistant electrode materials, which hinders the practical applications of seawater electrolysis. Therefore, intensive research efforts have been devoted to optimizing electrode materials using fundamental theories for practical applications. This review summarizes the recent progress in advanced electrode materials with an emphasis on their selectivity and anti-corrosivity. Practical materials with improved selectivity for oxygen generation, such as mixed metal oxides, Ni/Fe/Co-based composites, and manganese oxide (MnOx)-coated heterostructures, are reviewed in detail. Theoretically, alkaline environments (pH > 7.5) are preferred for OER as a constant potential gap (480 mV) exists in the high pH region. Nevertheless, corrosion of both the cathode and anode from ubiquitous Cl- is inevitable. Only a few materials with good corrosion resistance are capable of sustained operation in seawater systems; these include metal titanium and carbon-based materials. The corrosion process is usually accompanied by the formation of a passivated layer on the surface, but the aggressive penetration of Cl- can damage the whole electrode. Therefore, the selective inhibition of Cl- transport in the presence of a robust layer is critical to prevent continuous corrosion. Advances in anti-corrosion engineering, which encompasses inherently anti-corrosive materials, extrinsically protective coating, and in situ generated resistive species, are systematically discussed. Rational design can impart the material with good catalytic activity, stability, and corrosion resistance. Finally, we propose the following opportunities for future research: 1) screening of selective and anti-corrosive materials; 2) mechanism of competitive reactions and corrosion; 3) evaluation of anti-corrosive materials; 4) industrial-scale electrolysis with high current density; 5) optimization of experimental conditions; and 6) development of integrated electrolyzer devices. This review provides insights for the development of strategies aimed at tackling chlorine-related issues in seawater electrolysis.

Key words: Seawater electrolysis, Chlorine chemistry, Anti-corrosion, Selective electrocatalyst

MSC2000: 

  • O646